Asymmetrical thioindigoid dyestuff



Patented Feb. 5, 1935 ASYMMETRICAILVTHIOINDIGOID DYESTUFF Ernst Stiicklin,

land, as'signor Binningen, near Basel, Switzerto the firm Society of Chemical Industry in Basie, BaseLfSwitzerland NoioDra wiing. Application December 29, 1933,

Serial The present invention relates to asymmetrical indigoid dyestuffs of the general formula halogen wherein one a: represents halogen,and' the other :2 alkyl, and wherein further two of the letters m, n and 1' represent two carbonatoms adjacent to each other and at the same time appertain to an aromatic ring system, and the" third represents NH, C or S. 7

These asymmetrical indigoid dyestuffs are obtained by condensing hydroxythionaphthenes of the general formula halogen wherein one 3: represents halogen, and the other :1: alkyl, and wherein w represents a reactive group, such as O, halogen, product of the generalformula wherein 2 represents a reactive group, such as O, halogen, anil, 2H and NOH, and wherein two of the letters m, n and 1' represent two'c'arbonatoms adjacent to each other and at the same time appertain to an aromatic ring system, and the third represents NH, 0 or S, and, if desired, treating the dyestuffs obtainedwith halogenating agents, such as, for example, chlorine, bromine or suliuryl chloride. H e i Hydroxythionaphthenes of the above general formula are, for instance," 4,6-dichloro -7 methyl 3-hydroxythionaphthene, 4,6-dichloro-7-ethyl3- hydroxythionaphthene, "4, 7-dichloro-f6-methyl-3- hydroxythionaphthene, 4- bromo '6 chloro 7- methyl- 3 -hydroxythionaphthene, 4 chloro 6% I ro-7-bromo6-methyl-3 like, and the homologues and substitution prodanil, 2H and NO H with a;

No; 704,601. In Switzerland January 4, whi s, (01. 260-53) bromo- 7 -methyl 3 hydroxythionaphthene, 4- chloro-l-bromo-B- methyl 3 hydroxythionaphthene, i-b r o m o -7-chloro-6-methyl-3-hydroxythionaphthene, 4,6-dibromo-7Pmethyl-3-hydroxythionaphthene,4,7-dibromo-6-methyl-3 hydroxy- 5 thionaphthene, 4- b r o m o-6-chloro-7-methyl-3- hydroxythionaphthene-Z-carboxylic acid, 4-chlo- -hydroxythionaphthene- 2-carboxylic acid, 2-(para-dimethylamino-) anil of 4,6 dichloro- '7 -methyl- 3 -hydroxythionaph- 10 theme and 4,7dichloro-fi-methylthionaphthenequinone.

Products of thethird named general formula are, for instance, five-membered condensed ring systems, like isatins, naphthisatins, indoxyls, thionaphthenequinones, hydroxythionaphthenes, naphthohydroxythiophenes, anthracenethioindoxyls, anthraquinonethioindoxyls, acenaphthenequinones, phenanthrenequinones and the ucts, anils and halides thereof. a

The condensation takes place'by heating the components in a solvent-which may act as condensing agent.

The new dyestuffs may distinguish themselves in dyeing and printing animal fibers, such as, for example, wool and silk, or vegetable fibers, such as, for example, cotton or artificial silk from regenerated cellulose, by their great strength and their excellent fastness properties. They can be converted by known methods into leuco-ester salts.

The said hydroxythionaphthenes or their reactive 2-derivatives may be made by various methods; for example for making 4,6-dichloro-7- rnethy13-hydroxyth ionaphthene the following procedure may be adopted:-

From 1 amino-2,4-dichloro-5-methyl-6-benzenesulfonic acid there is obtained by diazotizing and conversion of the'diazo-compound thus obtained with cuprous cyanide the l-cyan-2: 4-dichloro-5-methyl-G-benzehesulfonic acid, which by the action of phosphorous pentachloride is converted into'the 1-cyan-2,4-dichloro-5-methyl- 6-benzenesulfochloride easily soluble in benzene. The sulfochloride is then reduced'and the mercaptan" thus 'formed is condensed without further purification in a weakly alkaline solution with monochloracetic acid. During the reduction the "cyanogen-group is simultaneously 'sapon'ified to the -CO-HN2 group. The 2,4-dichloro-5- methyl-6-phenylthioglycolcarboxylic acid-l-carboxylic acid amide thus obtained readily closes the ring already after a short boil in weakly alkaline solution to the 4,6-dichloro-7-methyl-3-hydroxythionaphthene, which crystallizes from alcohol in colorless needles of melting point 127 C.

The 4,? dichloro 6 methyl- 3 hydroxythionaphthene can be made from the l-amino-Z, 5- dichloro-4-methyl-6-benzenesulfonic acid in a manner quite analogous to that described for making the 4,6-dichloro-7-methyl-3-hydroxythionaphthene. It crystallizes from alcohol in colorless needles of melting point 145 C.

From the 3-hydroxythionaphthenes of the above general formula the reactive Z-derivatives,

such as, for example, the 2-anils 2-oximes, 2-

halides, are obtained in known manner by the interaction of nitroso compounds, nitrous acid or halogens. From the 2-anils the corresponding thionaphthenequinoneanils are obtained by saponification with, for example, sulfuric acid.

The following examples illustrate the invention, the parts being by weight- Example 1 233 parts of 4,6-dichloro-7-methyl-3-hydr0xythionaphthene and 326 parts of Z-(para-dimethylamino-)anil of 6-ethoxy-3-hydroxythionaph-- thene are heated to the boil, in 4000 parts of alco- 1101. After the condensation is complete the dyestuff of the formula co co \G=O/ c1- s s coin.

is filtered, ofl, washed and dried. It represents a bright scarlet red powder which dissolves in concentrated sulfuric acid to a blue-green solution.

- The dyestuff' forms a yellow vat and dyes cotton pure full scarlet tints of excellent fastness.

Example 2 is obtained in the form of a brown-red powder which dissolves in concentrated sulfuric acid to a blue-green solution and dyes cotton from a redyellow vat full pure red-brown tints.

Example 3 233 parts of 4,7-dichloro6methyl-3-hydroxythionaphthene are dissolved in 2000 parts 01' chlorobenzene and mixed at 70 C. with a solu tion of 5,7-dibromisatinchloride produced in known manner from 305 parts of 5,7 -dibromi satin and 250 parts of phosphorus pentachloride in chlorobenzene. After stirring for a short time the condensation is complete. After filtering, washing and drying the dyestufl of the formula is obtained in the form of a dark violet powder which dissolves in concentrated sulfuric acid to a green solution and dyes cotton from a yellow vat blue-violet tints;

By substituting in. this example 216 parts of 5:7-dichlorisatin for the 5,7-dibromisatin there is obtained, a dyatutf having similar properties.

A dyestufi possessing similar properties is ob- 2O tained by substitutmg in this example 233 parts of 4,6 dichloro '1;-methyl-3-hydroxythionaphthene for the 4,7-dichloro-6-methyl-3-hydroxythionaphthene used.

Example. 4

233 parts of 4,7-dichloro-fi -methyl-3-hydroxythionaphthene and 216 parts of 5,7-dichlorisatin are heated in 3000 parts of glacial acetic acid until the dyestuff formation is complete. After filtering, washing and drying the dyestufi of the formula I c1 c1 40 is obtained as a brown-red powder which dissolves in sulfuric acid to a blue-green solution and dyes cotton from a yellow vat red tints. 45

By substituting in this example equal parts of 4,6 dichloro-7-methyl-2-hydroxythionaphthene for the 4,7-dichloro-6-methyl-3 hydroxythionaphthene there is obtained a dyestuff having similar properties. 50

Example 5 233 parts of 4,7-dicl'rl0ro-6-methyl-3-hydroxythionaphthene and 222. parts of m-isatin-anilide are heated to boiling in 400.0 parts. of. alcohol. After the condensation is complete the dyestufl" of the formula one similar properties.

1,990,010 3. .Ewample6l' v. v(31- v V v 7 I oo furie acid, while cooling, and the solution thus Q I S 002m 362 parts of the dyestufi obtained in Example obtained is stirred with 130 parts of bromine,

5 are dissolved in 6000 parts of concentrated sulwhile slowly raising the temperature until the bromination is complete. The dyestuff which has precipitated by pouring the solution on ice is film tered, washed and dried. It represents a red- Y dish blue powder which dissolves in'concentrated f 00 0 O l sulfuric acid to a :blue-green solution and dyes cotton from a yellow vat reddish blue'tints. OH 8/ I \S 01 I 1 If in this example the 362 parts of the dyestufi 3 obtained in Example 5 are replaced by'429 parts of the dyestuff- No. X of the table, there is ob- H tained a violet dyestuff which dissolves in con- 0 I centrated sulfuric acid to a green solution and I dyes cotton from a red-yellow vat violet tints. Co CO C r 2 The following table displays further examples I 0 I =0 20.

of dyestuffs obtainable according to this inven- S/ \S 0 tion from 4,6-dichloro-'7-methyl-3-hydroxythio 7 1 naphthene or 4,7-dichloro-6-rnethyl-3-hydroxy- C1 I thionaphthene, respectively:-

a l V 25 Color in 4,6-diohloro-7-methyl-3-hydroxythionaphthene and:- cgg f g f sugg liic Color of the vat gg g tgg I. 2-(t1fiara-dimethylaminm) -anil of 4-metl1yl-6-ohloro-3-hydroxythionaph- Pink Green Yellow Pure pink B118. I 5 n II. 2-(trlalara-dimethylamind)Janil oi i metl yl-fi'ehlorot-hydroxythionaph- Red Green Green-yellow Red ene. I III. 2-(p1ara-din ethylamino0-anil of 5-chloro-7-methyl-3-hydroxythionaph- Red Green Green-yellow Red ene. l IV. 2-(para-dimethylamino-)-anil of 1-oh1 oro2,3-naphthioindoxyl. Violet Green Red-yellow v Violet 4,7-dioh1oro-6-metl1yl-3-hydroxythionaphthene-andz- 3'5 V. 2-(para-dimethylamino-)-a.nil of 6-ethoxy-3 hydroxythionaphthen Scarlet Green Yellow Soarlet VI. 2-ggara-dimethylaminofi-anil of4-methyl-6-chloro-3-hydroxy'tl1ionaph- Red Green Yellow Pml;

ene. V l l is 0 VII. Z-Egara-dimethylaminoO-anil oi 5-methyl-6-chloro-3-hydroxythionaph- Bed Green Yellow Red 40 6H9. 1

VIII. 2-(t flara-di1nethylarnino0-anil of 5-chloro-7-methy1-3-hydroxythionaph- Blue-red Green Yellow -Bluisl1 -red 6119. IX. 2-(para-dimethylamino-)-ani1 of 1,2-naphthioimioxyl.. Brown Blue-green 'Yellow Bordeaux X. 2-(para-dimethylamino-)-anil of 2,3-naphtl1ioindoxyl Blue Green Red-yellow Violet 43 The dyestuffs I to Xfof the foregoing table-corvm. 1 45 respond with the following formulas:'--- r l 1. 01 CH: oo oo 01 o p CH: s s r p CH3 1x. or 1r 01 I oo oo r o: v OH s Q1 p l t a Q1 I Ha 6ov III: Cl

O1 CH 65 CH: E l 7 W. 01 xamp e 5 parts of the dyestuff described in Example 2 70 are made into the paste with 20 parts of caustic soda solution of 33 per cent. strength. There are 01 then added 750 parts of water at 70 C. and 15 parts of sodium hydrosulfite the whole being allowed to stand for 30 minutes and then diluted to 2000 parts with water. parts of cotton are now entered into the bath at 60 C., 50 parts of common salt are added after about 10 minutes and dyeing is, continued for /2 hour at 60 C. The material is then washed, oxidized in the air for 30 minutes, rinsed and soaped. The cotton is thus dyed very fast red-brown tints. For wool, silk and artificial silk the dyeing process must of course be varied to suit the nature of these fibers.

What I claim is: v

1. Asymmetricalindigoid dyestuffs of the general formula halogen wherein one a: represents halogen, and the other 3: alkyl, wherein further R represents a benzene or naphthalene or anthracene radical which products form red to blue powders which dissolve in concentrated sulfuric acid to green solution, yield with hydrosulfite and caustic soda solution yellow vats, from which cotton is dyed fast red to blue tints.

2. Asymmetrical indigoid dyestuffs of the gen.- eral formula l'lalogen wherein one .1: represents halogen, and the other a: methyl, wherein furtherR represents a benzene or naphthalene or anthracene radical, which pro-ducts form red to blue powders which dissolve in concentrated sulfuric acid to green solutions, yield with hydrosulfite and yellow vats, from which cotton is dyed fast red to blue tints.

3. Asymmetrical indigoid dyestuffs of the general formula yield with hydrosulfite and caustic-soda solution yellow vats, from which cotton is: dyed fast red to blue tints.

caustic soda solution 4. Asymmetrical indigoid dyestuffs of the general formula 8/ I wherein one-a: represents chlorine, and the other a: methyl, wherein further R represents a benzene or naphthalene or anthracene radical, which products formred toblue powders which dissolve in concentrated sulfuricacid to green solutions, yield withhydrosulfite and caustic soda solution yellow vats, from which cotton is dyed fast red to blue tints.

5. Asymmetrical indigoicl, dyestuffs of the general formula wherein one .2: represents chlorine, and the other x: methyl, which: products. form red powders which product forms, a pink powder which dissolves in concentrated sulfuricacid to green solution, yields with hydrosulfite andcaustic soda solution a yellow vat, from which cotton is dyed pure pink tints.

7. An asymmetrical formula which product forms a. red powder which dissolves in concentrated sulfuric acid to a green solution, yields with hydrosulfite and caustic soda solution a yellow vat, from which cotton is dyed pink tints.

indigoid dyestufi of the ERNST STCCKLIN. 

